Process of spinning viscose artificial silk, filaments comprising threads, staple fibers, bands, and the like



Patented Oct. 12, 1948 PROCESS OF CIAL SPINNING VISCOSE ARTIFI- SILK,FILAMENTS COMPRISING THREADS, STAPLE FIBERS, BANDS, AND

THE LIKE Theeuwis Albertus Hendrikus Blaas, deceased, late of Nimeguen,Netherlands, by Johanna Geertrui Blaas, nee Westendorp, widow, Epse,Gorssel, Netherlands, assignor to Naamlooze VennootschapKunstzijdespinnerij Nyma, Nimeguen,

Netherlands No Drawing. Application January 30, 1946, Serial N0. 644,440In the Netherlands June 29, 1943 8 Claims. 1

The invention relates to an improvement in the process of spinningviscose artificial silk, filaments comprising threads, staple fibres,bands and the like and especially to a method for preventing theobstruction of the spinning nozzles, which is caused by the slowclogging of the orifices during spinning. The said obstruction isespecially serious when using a spinning bath containing zinc sulphate.

It has repeatedly been attempted to meet the said difficulty by theaddition to the spinning bath of surface-active substances. The additionhas been proposed to the spinning bath and/or to the viscose ofcompounds with a surface-active anion and also of compounds with asurface-active cation. The addition of a compound with a surface-activeanion does not bring about an appreciable improvement. A drawback of theaddition of compounds with a surface-active cation is that the presenceof these compounds in the spinning bath, where they accumulate either bydirect addition thereto or, when added to the viscose, during spinning,causes strong foam formation when the spinning bath is regenerated, Vizin the concentration thereof by evaporation. Another drawback is thatthe alkyl pyridinium salts which represent the best accessible class ofthese compounds are rapidly decomposed in the alkaline viscose so thatthey can only be used as an addition to the spinning bath.

It is an object of the invention to provide a method which ensuresregular spinning without obstruction of the nozzles. invention is theaddition of compounds which are stable in acid as well as in alkalineliquids. Still another object is not to use additions causing foamformation in concentrating the spinning bath by evaporation.

According to the invention small amounts of certain compounds or saltsof compounds are added to the spinning bath or to the spinning solutionor if desired to both, which do not reduce Another object of the whereinR represents an aromatic radical containing no more than 6 carbon atoms,R represents a substituent selected from a class consisting of hydrogen,aliphatic hydrocarbon groups containing no more than 2 carbon atoms andaryl groups containing no more than 6 carbon atoms, and X represents asubstituent selected from a group consisting of OH and a monovalent acidradical. Furthermore the pyridinium nucleus can be replaced by a homologor derivative of yridinium. The compounds in view canaccording to F.Krohnke, Ber. 67, 656 (1934); 68, 1351 (1935) be prepared frompyridinium or a homolog or derivative of'pyridi-nium, an alkali halidewhich may or may not be substituted and an aldehyde. Pyridinium halidesor other pyridinium salts with a'monovalent acid radical or compoundsfrom which such pyridinium salts can be formed under the reactioncircumstances can also be used as a starting material. Furthermore thecompounds to be used according to the invention can also be preparedfrom other starting materials, e. g. from styrene, bromohydrine or fromhomologs or derivatives of pyridinium.

The indicated compounds are generally spea ing not only stable indiluted acids, but also in cold diluted alkaline liquids and they cantherefore 1 be added to the viscose as well as to the spinning thesurface-tension of aqueous solutions and are a bath. The compounds notbeing surface-active there is no foam formation when concentrating thespinning bath in the regeneration thereof.

From the following examples elucidating the invention the beneficialeffect of the addition will become evident.

Example I N(a-furyl-2' hydroxy-Z phenyl-l' ethyl) -1 pyridiniumbromide.An equivalent amount of furfural is added to a solution ofbenzylpyridiniumbromide in ethanol. After the addition of 10 11. sodiumlye the reaction mixture is deposited during 5 days at 0 C. Theseparated product is washed with alcohol and treated with decolorizingcarbon and then recrystallized from waterof C. The product melts at 207C. under decomposition.

0.1% of this compound was dissolved in a spinning bath containing inaddition to normal quantities of sodium sulphate and sulphuric-acid, 50g. of zinc sulphate per litre. After spinning for about 1 hourmicroscopical examination proved that of the orifices was completelyclear,

' whereas in spinning under the same circumstances 3 but withoutaddition of the orifices proved to be clear.

Example II N(a-furyl-2 hydroxy-Z vinyl-1' ethyl) -1 pyridiniumbromide.

This compound is prepared from f-urfural and.

allylpyridiniumbromide. not sharply defined. The decomposition begins at140 C.

0.1% of this compound was dissolved in a spinning bath containing inad'd'iti'onfl'tothe normal amounts of sodium sulphate and.sulphuricjacid 50 g. of zinc sulphate per litre.

The 'melting point is After spinning. for about 8 hours the obstructionof the orifices amounts of sodium sulphate and sulphuric acid and 50g.01'- zinc-sulphate per litre.

After spinning for about 1 hour still over 60% of orifices wascompletely clear, whereas microscopical examination of the nozzles afterspinning in a bath of the same. composition but without addition provedthat only 10% of the orifices was still clear.

Example IV N-( phenyl- 2 hydroxy-2' vinyl-1' ethyl) -1 pyridiniumbromide was prepared from allylpyridiniumbromideand benzaidenyde. 0.1%of this com' pound was added to viscose and spinning took place in abath with normal amounts 'of sodium sulphate and sulphuric acid. and 50g. of zinc sulphate per litre.

After'spinning' for about 1 hour microscopical I examination'provedthatover 80% of theorifices was still-completelyclear. In checking thenozzles aft-er spinning in a ba'tl'rof the samecompos'itirm but withoutaddition 0% of the orifices appeared to-be clear att'erthe same durationof spinning.

' Example V N (phenyl-2' hydroxy-2' vinyl-'1" ethyl)--:1:pyridinium'chlorid'e was prepared from allylpyridin iumchlorideandbenzaldehyde.

0.1% of this compound was-dissolved ina spin-- ning bath as describedabove. .After spinning during 8 hours microscopicalexamination provedthat still over 90% of the orifices was completely clear, whereas only10% of the orifices in the nozzles used in comparative tests,.wherein-the same viscose was spun i-n the-same bath, without additionhowever, did not show obstruction.

Erample VI 7 0.07% of Nfphenyl 2" hydroxy 2' vinyl 1' ethyD-lpyridin'iumchloride is added to viscose and the viscose is extruded intoa bath with normal sodium sulphate and sulphuricacid content and 50 g.01' zinc sulphate per'litre, e

After spinning. during about /4 of an hour microscopical examinationproves that still 95% of the orifices is completely clear; whereas innozzles used for spinning of a normal viscose in V a spinning batl'i ofthe same composition only about T0% of the orifices was still clear.

4" V The structural formulae of the compounds of. Examples I to VI are:

Example! Ht. that Example II H N-Br e H H H Example V Example VI wt-taHHH Itwill be' understood that the invention is not limited :tothecompounds, amounts added, spinning; baths used or other data given byway of examples in the above modes of proceeding.

Having thus described the invention What is desired to-secure byLetters'Patent and claimed:

1. In the spinning of viscose, employing spin- I ning nozzles which tendto become clogged, the process which comprises preventing such clogg-ingby adding to at-least-one of theliquids which come into contact withsaid-nozzlesduring spi-nningia-small amount ofa pyridi-n -compound whichisnot surface active. of the general formula:

wherein R represents an aromatic radical containing no more than 6carbon atoms, R represents a substituent selected from a classconsisting of hydrogen, aliphatic hydrocarbon groups containing no morethan 2 carbon atoms and aryl groups containing no more than 6 carbonatoms, and X represents a substituent selected from a group consistingof OH and a monovalent acid radical.

2. The process of claim 1 wherein R represents a vinyl radical.

3. The process of claim 1 wherein R represents phenyl.

4. The process of claim 1 wherein R represents a furyl radical.

5. The process of claim 1 wherein R represents phenyl.

6. The process of claim 1 wherein the quantity of pyridine compoundadded is sufiiclent to produce a concentration of the order of 0.1 percent by Weight.

7. Process for producing artificial filaments, threads, fibres, staplefibres and the like from viscose, comprising the addition, in any stageof the process, to at least one of the liquids coming into contact withthe nozzles during spinning of 0.1% of N(a-furyl-2' hydroXy-2 vinyl-1ethyl) -1 pyridiniumbromide,

i t @t rr OH H H JOHANNA GEERTRUI BLAAS NE'IE WESTENDORP, Personalrepresentative authorized to file patent applications on behalf ofTheeuwz's Albertus Hendrz'lcas Blaas, Deceased.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,125,031 Polak July 26, 1938FOREIGN PATENTS Number Country Date 641,270 Germany Jan. 26, 1937641,271 Germany Jan. 26, 1937

